CN111003692A - Sulfur dioxide recycling system and method - Google Patents

Sulfur dioxide recycling system and method Download PDF

Info

Publication number
CN111003692A
CN111003692A CN201911286382.8A CN201911286382A CN111003692A CN 111003692 A CN111003692 A CN 111003692A CN 201911286382 A CN201911286382 A CN 201911286382A CN 111003692 A CN111003692 A CN 111003692A
Authority
CN
China
Prior art keywords
sulfur
gas
output end
reaction kettle
sea wave
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911286382.8A
Other languages
Chinese (zh)
Other versions
CN111003692B (en
Inventor
徐海涛
徐延忠
李明波
陈任远
刘大华
吴振山
宋静
徐梦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Deyitong Environmental Protection Technology Co ltd
Nanjing Jiekefeng Environmental Protection Technology Equipment Research Institute Co ltd
Nanjing Liuyan Environmental Protection Technology Co ltd
Nanjing Tech University
Original Assignee
Jiangsu Deyitong Environmental Protection Technology Co ltd
Nanjing Jiekefeng Environmental Protection Technology Equipment Research Institute Co ltd
Nanjing Liuyan Environmental Protection Technology Co ltd
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Deyitong Environmental Protection Technology Co ltd, Nanjing Jiekefeng Environmental Protection Technology Equipment Research Institute Co ltd, Nanjing Liuyan Environmental Protection Technology Co ltd, Nanjing Tech University filed Critical Jiangsu Deyitong Environmental Protection Technology Co ltd
Priority to CN201911286382.8A priority Critical patent/CN111003692B/en
Publication of CN111003692A publication Critical patent/CN111003692A/en
Priority to US17/784,264 priority patent/US11731874B2/en
Priority to PCT/CN2020/089515 priority patent/WO2021114561A1/en
Application granted granted Critical
Publication of CN111003692B publication Critical patent/CN111003692B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/021—Separation of sulfur from gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • B01D5/0072—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0078—Condensation of vapours; Recovering volatile solvents by condensation characterised by auxiliary systems or arrangements
    • B01D5/0093—Removing and treatment of non condensable gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80—Semi-solid phase processes, i.e. by using slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/0232—Purification, e.g. degassing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
    • C01B17/0482—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon or solid carbonaceous materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/64—Thiosulfates; Dithionites; Polythionates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/14—Preparation of sulfites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/608—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Abstract

The method comprises main functional equipment such as the carbon reduction furnace, the high-temperature dust remover, the cooling separator A, the liquid sulfur box, the cooling separator B, the tail gas absorption tower, the gas stripping tower, the sea wave reaction kettle, the centrifuge, the mother liquor tank, the thickener and the like, and comprises the steps of preparing ① elemental sulfur, removing dust of ② process gas containing gaseous sulfur, separating ③ elemental sulfur, and ④. residual SO2Reabsorbing gas, ⑤, purifying powdered sulfur, preparing ⑥ seawave clinker slurry, ⑦ separating liquid from solid, ⑧ preparing absorption slurry and other steps, and treating SO2The gas is reduced into liquid sulfur and powdered sulfur, and SO is avoided by co-producing sodium thiosulfate2The pollution problem of the by-product in the sulfur production is solved, no waste water is generated, and SO is removed2The primary conversion rate of gas sulfur production is not highThe problem of (2) can greatly reduce the overall investment of the system, improve the operation flexibility of the system and lead the SO2The sulfur production technology has the possibility of practical application.

Description

Sulfur dioxide recycling system and method
Technical Field
The invention relates to the field of chemical industry, in particular to a sulfur dioxide resource recovery system and a sulfur dioxide resource recovery method.
Background
Sulfur dioxide emitted from industrial waste gas is up to hundreds of millions of tons every year, and conventional desulfurization or sulfur fixation technologies form desulfurization byproducts, such as gypsum, magnesium sulfate, ammonium sulfate, sulfuric acid, sodium sulfate and the like. At present, desulfurized gypsum, magnesium sulfate, sodium sulfate and the like mainly adopt wastes, and high cost is required to be invested for secondary treatment; although ammonium sulfate, sulfuric acid and the like have certain economic values, the excess production energy of related products is large, and the value of byproducts is far awayBelow the production cost, the two desulfurization process routes described above remain to be claimed continuously both currently and for a long time in the future. Meanwhile, the waste gas recycling technology has been proposed for many years, and the best technical route is known to be that sulfur dioxide is directly reduced into elemental sulfur, but the SO is treated by the fact that the market economy is limited by the fact that the primary reduction efficiency of sulfur dioxide is not high2The exhaust gas technology still fails to bypass the above technical range, and the realization of desulfurization of secondary pollutants or high desulfurization cost is still in the continuing.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sulfur dioxide resource recycling technology, which utilizes a carbonaceous reducing agent easily obtained in the market to directly recycle SO2The high-efficiency reduction is carried out, and industrial products with high added values such as elemental sulfur, sodium thiosulfate and the like are obtained as byproducts, and the method has the characteristics of relatively low system investment, smooth sales of the byproducts and no secondary waste.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a sulfur dioxide resource recovery system comprises a gas output end of a carbonaceous reduction furnace connected with a high-temperature dust remover, wherein one gas phase output end of the high-temperature dust remover is connected with a cooling separator A, and the other gas phase output end of the high-temperature dust remover is connected with a cooling separator B;
the liquid phase output end of the cooling separator A is connected with the liquid sulfur tank, the gas phase output end of the cooling separator A is connected with the thickener through the tail gas absorption tower, the output end of the thickener is respectively connected with the sea wave reaction kettle, the centrifugal machine and the mother liquor tank, the sea wave reaction kettle is connected with the mother liquor tank through the centrifugal machine, and the output end of the mother liquor tank is respectively connected with the thickener and the tail gas absorption tower;
the gas phase output end of the cooling separator B is connected with the tail gas absorption tower, the solid phase output end of the cooling separator B is connected with the gas stripping tower, the gas stripping tower is connected with the centrifugal machine through the sea wave reaction kettle, the solid phase output end of the centrifugal machine is a product, and the liquid phase output end of the centrifugal machine is connected with the mother liquor tank.
In the above system: the solid phase output end of the high temperature dust remover and the gas output end of the gas stripping tower are connected with the carbonaceous reducing furnace.
In the above system: the gas stripping tower is also provided with a gas stripping gas input pipeline and a sulfur powder output pipeline.
In the above system: the sea wave reaction kettle is provided with a sodium alkali input pipeline, and the mother liquor tank is provided with a sodium alkali and process water input pipeline.
A method for realizing sulfur dioxide resource recovery by the system comprises the following steps:
① preparation of elemental sulfur by using carbonaceous reducing agent and SO in carbonaceous reducing furnace2Carrying out oxidation-reduction reaction on the raw flue gas to generate a process gas containing gaseous sulfur, and controlling the volume content of oxygen in the process gas to be lower than 1.5%;
② dedusting the process gas containing gaseous sulfur by dedusting the dust and sulfur vapor in ① process gas containing gaseous sulfur in a high temperature deduster by using a filter element;
③, separating elemental sulfur, namely, feeding the process gas containing gaseous sulfur after dust removal in the step ② into a condensation separator A and/or a condensation separator B for separation, separating liquid sulfur through the condensation separator A, and separating fine sulfur through the condensation separator B;
④ residual SO2Re-absorbing the gas, namely absorbing and purifying the non-condensable gas which is discharged from the condensation separator A and/or the condensation separator B in the step ③ by using a tail gas absorption tower, wherein the pH value of absorption liquid of the absorption tower is controlled to be more than 6.5;
⑤, purifying the powdered sulfur, namely, feeding the powdered sulfur obtained in the step ③ into a stripping tower, wherein the stripping tower adopts low-pressure nitrogen and/or purified tail gas at the outlet of a tail gas absorption tower as stripping media, one part of the sulfur powder after stripping is conveyed into a sea wave reaction kettle, and the other part of the sulfur powder is output as a product;
⑥ preparation of sea wave clinker slurry, transferring the absorption liquid absorbed by the absorption tower to a thickener, placing the thick slurry in a sea wave reaction kettle, adjusting pH to 10 with sodium alkali, and controlling Na in the sea wave reaction kettle2SO3And H2The molar ratio of O is 1: (6.3-7.5), and simultaneously according to the following S: na (Na)2SO3The molar ratio is 1: (1.1-1.2) adding sulfur powder, and sealingHeating and curing the sea wave reaction kettle to obtain suspension;
or the sulfur powder is not added into the sea wave reaction kettle, and the sodium sulfite slurry is directly produced, which comprises the following steps:
preparation of sodium sulfite slurry: conveying the absorption liquid absorbed by the absorption tower into a thickener, putting the slurry into a sea wave reaction kettle, and adjusting the pH value to 10 by using sodium alkali to obtain sodium sulfite slurry;
⑦, liquid-solid separation, namely, conveying the suspension obtained by heating and curing in the step ⑥ into a centrifugal machine, and separating by the centrifugal machine to obtain a wet product of sodium thiosulfate and a mother solution of sodium thiosulfate;
or sending the sodium sulfite slurry into a centrifuge, and separating by the centrifuge to obtain a sodium sulfite wet product and a sodium sulfite mother liquor;
⑧, preparing absorption slurry by using mother liquor, process water and sodium alkali to prepare absorption liquid with the pH value of 10-12 and the relative density of 1.28-1.40, and conveying the absorption liquid to a tail gas absorption tower and a thickener.
In the method, the carbon reduction furnace in the step ① can be divided into an ash cooling section and an SO cooling section from top to bottom according to the temperature during working2A reducing section and a reducing agent preheating section; preferably: the temperature of the lower part of the ash cooling section is controlled to be 250-380 ℃ and SO2The temperature of the reduction section is controlled to be 860-1100 ℃, and the temperature of the upper part of the reducing agent preheating section is controlled to be 380-650 ℃.
In the method, in step ①, the carbonaceous reducing agent and the sulfur-containing flue gas SO2Has a mass metering ratio of M1:M21 (2-8), wherein M1Mass flow rate of fixed carbon in carbonaceous reducing agent, M2For SO in sulfur-containing flue gas2Mass flow rate of (d); preferably: the molar ratio S (0) of zero-valent sulfur to positive tetravalent sulfur in the process gas containing gaseous sulfur discharged from the carbonaceous reducing furnace is S (IV): 1.3-95: 1; further preferably: in the case of sulfur dusting, S (0): the ratio of S (IV) is not less than 1.05, and when sodium thiosulfate is generated, S (0): the ratio of S (IV) is controlled to be 1.05-1.08.
In the method, the temperature of the process gas containing gaseous sulfur entering the high-temperature dust remover in the step ② is 380-650 ℃, and the temperature drop of the gas before and after entering the high-temperature dust remover is not more than 30 ℃.
In the method, the condensation separator A in the step ③ uses process hot water at 103-108 ℃ or process gas at 70-105 ℃ as a cooling medium to cool the process gas containing the gaseous sulfur to 105-113 ℃, and the condensation separator B uses process water at 15-100 ℃ or process gas at less than 80 ℃ as a cooling medium to cool the process gas containing the gaseous sulfur to below 105 ℃.
In the method, the stirring is carried out in the heating and curing process in the step ⑤, the stirring speed is adjusted to 26-35 r/min, the reaction temperature is controlled to be 100-105 ℃, and the reaction time is controlled to be 30-45 min.
The method comprises the following steps: the carbonaceous reducing agent used in the process is a mixture of one or more substances of white coal, carbon powder, coke, high-sulfur coal and petroleum coke, and the sodium alkali used in the process is sodium carbonate, sodium hydroxide or a sodium hydroxide solution with the mass concentration of 30-50%.
The invention has the beneficial effects that:
① A set of process system can produce multiple products as by-products, and can adjust production liquid sulfur, powder sulfur, sodium sulfite, sodium thiosulfate and other products as required;
② Co-production of sodium thiosulfate and solves the problem of SO2The problem of low primary conversion rate of sulfur production by gas can greatly reduce the overall investment of the system, improve the operation flexibility of the system and lead SO2The sulfur production technology has the possibility of practical application;
③ avoid SO2The pollution problem of the by-product in the sulfur production is solved, and no waste water is generated;
④ the tail gas is absorbed by sodium alkali slurry, SO as to ensure SO in the tail gas2Ultra-low emission.
Drawings
FIG. 1 is a schematic flow diagram of the inventive system.
Wherein: 1 is a reduction furnace, 2 is a high-temperature dust remover, 3 is a cooling separator A, 4 is a liquid sulfur tank, 5 is a cooling separator B, 6 is a tail gas absorption tower, 7 is a stripping tower, 8 is a sea wave reaction kettle, 9 is a centrifugal machine, and 10 is a mother liquor tank.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
referring to fig. 1, a sulfur dioxide resource recovery system comprises a gas output end of a carbonaceous reduction furnace 1 connected with a high-temperature dust remover 2, one output end of the high-temperature dust remover 2 is connected with a cooling separator A3, and the other output end is connected with a cooling separator B5;
the liquid output end of the cooling separator A3 is connected with the liquid sulfur tank 4, the gas output end is connected with the thickener 11 through the tail gas absorption tower 6, the output end of the thickener 11 is respectively connected with the sea wave reaction kettle 8, the centrifuge 9 and the mother liquor tank 10, the sea wave reaction kettle 8 is connected with the mother liquor tank 10 through the centrifuge 9, and the output end of the mother liquor tank 10 is respectively connected with the thickener 11 and the tail gas absorption tower 6;
the gas phase output end of the cooling separator B5 is connected with the tail gas absorption tower 6, the solid phase output end of the cooling separator B5 is connected with the gas stripping tower 7, the gas stripping tower 7 is connected with the centrifuge 9 through the sea wave reaction kettle 8, the solid phase output end of the centrifuge 9 is a product, and the liquid phase output end is connected with the mother liquor tank 10.
The solid phase output end of the high temperature dust remover 2 and the gas phase output end of the gas stripping tower 7 are both connected with the carbonaceous reduction furnace 1. The carbonaceous reduction furnace 1 is provided with SO2A raw material gas input pipeline, a carbonaceous reducing agent input pipeline and a solid residue output pipeline arranged at the bottom. The gas stripping tower 7 is also provided with a gas stripping gas input pipeline and a sulfur powder output pipeline. The sea wave reaction kettle 8 is provided with a sodium alkali input pipeline, and the mother liquor tank 10 is provided with a sodium alkali and process water input pipeline.
A method for recycling sulfur dioxide by using the system, as in examples 1-3.
EXAMPLE 1 Synthesis of sodium thiosulfate and Sulfur powder
① preparation of elemental sulfur by using white coal, carbon, coke, high-sulfur coal or petroleum coke as conventional carbon reducer and SO in carbon reduction furnace2The raw flue gas is subjected to oxidation-reduction reaction to generate a process gas containing gaseous sulfur, and the volume content of oxygen in the process gas is controlled to be lower than 1.5%. In thatThe carbon reduction furnace can be divided into an ash cooling section and an SO cooling section from top to bottom according to the temperature2The temperature of the lower part of the reduction section, the reducing agent preheating section and the ash cooling section is controlled to be 250-380 ℃ and SO2The temperature of the reduction section is controlled to be 860-1100 ℃, and the temperature of the upper part of the reducing agent preheating section is controlled to be 380-650 ℃; carbonaceous reducing agent and sulfur-containing flue gas SO2The mass metering ratio of (A) is M1: M2 ═ 1 (3-8), wherein M is1Mass flow rate of fixed carbon in carbonaceous reducing agent, M2For SO in sulfur-containing flue gas2Mass flow rate of (d);
s (0) of the process gas containing gaseous sulfur discharged from the carbonaceous reduction furnace: and (1.05-95) 1, wherein: in the case of sulfur dusting, S (0): the ratio of S (IV) is not less than 1.05, and when sodium thiosulfate is generated, S (0): the ratio of S (IV) is controlled to be 1.05-1.08.
② dedusting the process gas containing gaseous sulfur, namely separating dust and sulfur vapor in the process gas containing gaseous sulfur in the step ① by using filter elements such as ceramic filter elements and metal filter elements, wherein the temperature of the process gas containing gaseous sulfur entering the high-temperature deduster is 380-650 ℃, and the content of dust particles in the process gas containing gaseous sulfur exiting the high-temperature deduster is 20mg/m3And the temperature drop of the gas before and after entering and exiting the high-temperature dust remover is not more than 30 ℃.
③, separating elemental sulfur, namely, sending the process gas containing gaseous sulfur in the step ② into a condensation separator B, cooling the process gas containing gaseous sulfur to below 105 ℃ in the condensation separator B by utilizing process water at 15-100 ℃ or process gas at the temperature of less than 80 ℃, and separating powdered sulfur.
④ residual SO2Absorbing and purifying the non-condensable gas out of the condensation separator B in the step ③, controlling the pH value of the absorption tower to be more than 6.5, and discharging SO in the purified gas out of the tail gas absorption tower2The content is less than or equal to 10mg/m3The dust content is less than or equal to 10mg/m3。
⑤, purifying the powdered sulfur, namely feeding the powdered sulfur obtained in the step ③ into a gas stripping tower, wherein the gas stripping tower adopts low-pressure nitrogen and purified tail gas at the outlet of a tail gas absorption tower as a gas stripping medium, the gas stripping medium is heated to 103-110 ℃ and enters the gas stripping tower from the bottom of the gas stripping tower, the dry basis mass fraction of elemental sulfur in the sulfur powder discharged from the gas stripping tower is not less than 99.6%, the sulfur powder is fed into a sea wave reaction kettle, and surplus sulfur powder is stored or packed out.
⑥ preparation of sea wave clinker slurry, which comprises transferring the absorption liquid of the tail gas absorption tower into a thickener, placing the thick slurry in the thickener into a sea wave reaction kettle, adjusting pH to 10 with sodium alkali, and controlling Na in the sea wave reaction kettle2SO3And H2The molar ratio of O is 1: (6.3 to 7.5) and Na as the molar ratio of S to Na2SO3The molar ratio is 1: (1.1-1.2) adding sulfur powder. And sealing the sea wave reaction kettle, controlling the stirring speed to be 26-35 r/min, the reaction temperature to be 100-105 ℃, and the reaction time to be 30-45 min.
⑦, liquid-solid separation, namely cooling the suspension obtained in the step ⑥ to below 50 ℃, then sending the suspension into a centrifuge, and separating by the centrifuge to obtain a wet product of sodium thiosulfate and a mother solution of sodium thiosulfate.
⑧, preparing absorption slurry by using mother liquor, process water and sodium alkali to prepare the absorption solution with the pH value of 10-12 and the relative density of 1.28-1.40.
Product index of the obtained sodium thiosulfate
Figure BDA0002318082940000051
Raw material in and out analysis
Figure BDA0002318082940000052
Figure BDA0002318082940000061
Index of sulfur powder
Purity of elemental sulfur Ash content Median diameter Moisture content Heavy metals (in Pb)
％ ％ μm ％ ％
≥99.2 ＜0.02 115～140 ＜0.2 ＜0.0005
Example 2 sodium thiosulfate and liquid sulfur
① preparation of elemental sulfur by using white coal, carbon, coke, high-sulfur coal or petroleum coke as conventional carbon reducer and SO in carbon reduction furnace2The raw flue gas is subjected to oxidation-reduction reaction to generate a process gas containing gaseous sulfur, and the volume content of oxygen in the process gas is controlled to be lower than 1.5%. In the carbon reduction furnace, the furnace can be divided into an ash cooling section and SO from top to bottom according to the temperature2The temperature of the lower part of the reduction section, the reducing agent preheating section and the ash cooling section is controlled to be 250-380 ℃ and SO2The temperature of the reduction section is controlled to be 860-1100 ℃, and the temperature of the upper part of the reducing agent preheating section is controlled to be 380-650 ℃; carbonaceous reducing agent and sulfur-containing flue gas SO2The mass metering ratio of M1 to M2 is 1 (2-8), wherein M1 is the mass flow of fixed carbon in the carbonaceous reducing agent, and M2 is SO in the sulfur-containing flue gas2Mass flow rate of (d); s (0) of the process gas containing gaseous sulfur discharged from the carbonaceous reduction furnace: and (1.05-1.20) S (IV) is 1.
② dedusting of a process gas containing gaseous sulphur, in accordance with example 1.
③ separation of elemental sulphur the gaseous sulphur-containing process gas from stage ② is fed into a condensation separator A and a condensation separator B, wherein the total amount of elemental sulphur in the gaseous sulphur-containing process gas fed into the condenser B is equal to the SO in the gaseous sulphur-containing process gas leaving the high temperature precipitator2The total amount of the organic solvent is in a constraint relation that the molar ratio is between 1.05 and 1.10.
Wherein: in the case of sulfur dusting, S (0): the ratio of S (IV) is not less than 1.05, and when sodium thiosulfate is generated, S (0): the ratio of S (IV) is controlled to be 1.05-1.08.
Cooling the process gas containing gaseous sulfur to 105-113 ℃ in a condensation separator A by using process hot water at 103-108 ℃ or process gas at 70-105 ℃, and separating liquid sulfur; and (3) cooling the process gas containing the gaseous sulfur to below 105 ℃ by utilizing process water at the temperature of 15-100 ℃ or process gas at the temperature of less than 80 ℃ in a condensation separator B, and separating out the powdered sulfur.
④ residual SO2And (4) reabsorption of gas. In accordance with example 1.
⑤, purifying powdered sulfur, namely feeding the powdered sulfur obtained in the step ③ into a stripping tower, wherein the stripping tower adopts low-pressure nitrogen and purified tail gas at the outlet of a tail gas absorption tower as stripping media, the stripping media are heated to 103-110 ℃ and enter the stripping tower from the bottom of the stripping tower, the dry basis mass fraction of elemental sulfur in the sulfur powder discharged from the stripping tower is not less than 99.6%, the sulfur powder is fed into a sea wave reaction kettle, and redundant sulfur powder is stored or doped with a carbonaceous reducing agent and returns to a carbonaceous reduction furnace again, or the proportion of process gas containing gaseous sulfur entering a condensation separator A is adjusted to produce liquid sulfur.
⑥ preparation of a Haibop clinker slurry consistent with example 1.
⑦ solid-liquid separation, in accordance with example 1.
⑧ absorbent slurry was prepared in accordance with example 1.
Index of obtained liquid sulfur product
Product index of the obtained sodium thiosulfate
Figure BDA0002318082940000071
Raw material in and out analysis
SO2Recovery rate C utilization rate SO2 content in tail gas Discharge of waste water
％ ％ mg/m3 t/t-SO2
99.98 65～75％ ＜10 0
Index of liquid sulfur
Purity of elemental sulfur Ash content Acidity (in terms of sulfuric acid) Moisture content Heavy metals (in Pb)
％ ％ ％ ％ ％
≥99.2 ＜0.02 ＜0.01 ＜0.2 ＜0.0005
Example 3 preparation of liquid Sulfur and sodium sulfite
① preparation of elemental sulfur by using conventional carbon reducing agent such as white coal, carbon powder, coke, high sulfur coal, petroleum coke, etc. and SO in a carbon reducing furnace2The raw flue gas is subjected to oxidation-reduction reaction to generate a process gas containing gaseous sulfur, and the volume content of oxygen in the process gas is controlled to be lower than 1.5%. In the carbon reduction furnace, the furnace can be divided into an ash cooling section and SO from top to bottom according to the temperature2The temperature of the lower part of the reduction section, the reducing agent preheating section and the ash cooling section is controlled to be 250-380 ℃ and SO2The temperature of the reduction section is controlled to be 860-1100 ℃, and the temperature of the upper part of the reducing agent preheating section is controlled to be 380-650 ℃; carbonaceous reducing agent and sulfur-containing flue gas SO2The mass metering ratio of M1 to M2 is 1 (2-8), wherein M1 is the mass flow of fixed carbon in the carbonaceous reducing agent, and M2 is SO in the sulfur-containing flue gas2Mass flow rate of (d); s (0) of the process gas containing gaseous sulfur discharged from the carbonaceous reduction furnace: (1.05-95) 1, preferably sulfur powder, wherein S (0): the ratio of S (IV) is not less than 1.05.
② dedusting of a process gas containing gaseous sulphur, in accordance with example 1.
③, separating elemental sulfur, namely, feeding the process gas containing gaseous sulfur in the step ② into a condensation separator A, cooling the process gas containing gaseous sulfur to 105-113 ℃ in the condensation separator A by using process hot water at 103-108 ℃ or process gas at 70-105 ℃, and separating liquid sulfur.
④ residual SO2And (4) reabsorption of gas. In accordance with example 1.
⑤ preparation of sodium sulfite slurry, controlling the pH value of the tail gas absorption tower to be above 7.5, adding alkali liquor into the thickener, and adjusting the pH value to 10.
⑥, liquid-solid separation, namely, sending the suspension obtained in the step ⑤ into a centrifuge, and separating by the centrifuge to obtain a wet product of sodium sulfite and a mother solution of sodium sulfite.
⑦, preparing absorption slurry by using mother liquor, process water and sodium alkali to prepare the absorption solution with the pH value of 10-12 and the relative density of 1.28-1.32.
Index of the obtained sodium sulfite product
Purity of pH of the solution Clarity of the product Iron content (in terms of Fe) Heavy metals (in Pb)
％ -- -- ％ ％
≥97.5 7.8～9.6 By experiment ＜0.0003 ＜0.001
Index of liquid sulfur
Purity of elemental sulfur Ash content Acidity (in terms of sulfuric acid) Moisture content Heavy metals (in Pb)
％ ％ ％ ％ ％
≥99.2 ＜0.02 ＜0.01 ＜0.2 ＜0.0005

Claims (10)

1. The utility model provides a sulfur dioxide resource recovery system which characterized in that: the system comprises a gas output end of a carbonaceous reduction furnace (1) connected with a high-temperature dust remover (2), one gas phase output end of the high-temperature dust remover (2) connected with a cooling separator A (3), and the other gas phase output end connected with a cooling separator B (5);
the liquid phase output end of the cooling separator A (3) is connected with the liquid sulfur tank (4), the gas phase output end is connected with the thickener (11) through the tail gas absorption tower (6), the output end of the thickener (11) is respectively connected with the sea wave reaction kettle (8), the centrifuge (9) and the mother liquor tank (10), the sea wave reaction kettle (8) is connected with the mother liquor tank (10) through the centrifuge (9), and the output end of the mother liquor tank (10) is respectively connected with the thickener (11) and the tail gas absorption tower (6);
the gas phase output end of the cooling separator B (5) is connected with the tail gas absorption tower (6), the solid phase output end of the cooling separator B (5) is connected with the stripping tower (7), the stripping tower (7) is connected with the centrifuge (9) through the sea wave reaction kettle (8), the solid phase output end of the centrifuge (9) is a product, and the liquid phase output end is connected with the mother liquor tank (10).
2. The sulfur dioxide resource recovery system of claim 1, characterized in that: the solid phase output end of the high temperature dust remover (2) and the gas output end of the gas stripping tower (7) are connected with the carbonaceous reducing furnace (1).
3. The sulfur dioxide resource recovery system of claim 1, characterized in that: the gas stripping tower (7) is also provided with a gas stripping gas input pipeline and a sulfur powder output pipeline.
4. The sulfur dioxide resource recovery system of claim 1, characterized in that: the sea wave reaction kettle (8) is provided with a sodium alkali input pipeline, and the mother liquor tank (10) is provided with a sodium alkali and process water input pipeline.
5. A method for recycling sulfur dioxide resource by using the system of claim 1, which is characterized in that: the method comprises the following steps:
① preparation of elemental sulfur by using carbonaceous reducing agent and SO in carbonaceous reducing furnace2OfCarrying out oxidation-reduction reaction on the flue gas to generate a process gas containing gaseous sulfur, and controlling the volume content of oxygen in the process gas to be lower than 1.5%;
② dedusting the process gas containing gaseous sulfur by dedusting the dust and sulfur vapor in ① process gas containing gaseous sulfur in a high temperature deduster by using a filter element;
③, separating elemental sulfur, namely, feeding the process gas containing gaseous sulfur after dust removal in the step ② into a condensation separator A and/or a condensation separator B for separation, separating liquid sulfur through the condensation separator A, and separating fine sulfur through the condensation separator B;
④ residual SO2Re-absorbing the gas, namely absorbing and purifying the non-condensable gas which is discharged from the condensation separator A and/or the condensation separator B in the step ③ by using a tail gas absorption tower, wherein the pH value of absorption liquid of the absorption tower is controlled to be more than 6.5;
⑤, purifying the powdered sulfur, namely, feeding the powdered sulfur obtained in the step ③ into a stripping tower, wherein the stripping tower adopts low-pressure nitrogen and/or purified tail gas at the outlet of a tail gas absorption tower as stripping media, one part of the sulfur powder after stripping is conveyed into a sea wave reaction kettle, and the other part of the sulfur powder is output as a product;
⑥ preparation of sea wave clinker slurry, transferring the absorption liquid absorbed by the absorption tower to a thickener, placing the thick slurry in a sea wave reaction kettle, adjusting pH to 10 with sodium alkali, and controlling Na in the sea wave reaction kettle2SO3And H2The molar ratio of O is 1: (6.3-7.5), and simultaneously according to the following S: na (Na)2SO3The molar ratio is 1: (1.1-1.2) adding sulfur powder, sealing the sea wave reaction kettle, and heating and curing to obtain suspension;
or the sulfur powder is not added into the sea wave reaction kettle, and the sodium sulfite slurry is directly produced, which comprises the following steps:
preparation of sodium sulfite slurry: conveying the absorption liquid absorbed by the absorption tower into a thickener, putting the slurry into a sea wave reaction kettle, and adjusting the pH value to 10 by using sodium alkali to obtain sodium sulfite slurry;
⑦, liquid-solid separation, namely, conveying the suspension obtained by heating and curing in the step ⑥ into a centrifugal machine, and separating by the centrifugal machine to obtain a wet product of sodium thiosulfate and a mother solution of sodium thiosulfate;
or sending the sodium sulfite slurry into a centrifuge, and separating by the centrifuge to obtain a sodium sulfite wet product and a sodium sulfite mother liquor;
⑧, preparing absorption slurry by using mother liquor, process water and sodium alkali to prepare absorption liquid with the pH value of 10-12 and the relative density of 1.28-1.40, and conveying the absorption liquid to a tail gas absorption tower and a thickener.
6. The method according to claim 5, wherein the carbonaceous reduction furnace in step ① is divided into ash cooling zone and SO cooling zone from top to bottom according to temperature2A reducing section and a reducing agent preheating section; preferably: the temperature of the lower part of the ash cooling section is controlled to be 250-380 ℃ and SO2The temperature of the reduction section is controlled to be 860-1100 ℃, and the temperature of the upper part of the reducing agent preheating section is controlled to be 380-650 ℃.
7. The method according to claim 5, wherein the carbonaceous reducing agent and the sulfur-containing flue gas SO in step ①2Has a mass metering ratio of M1:M21 (2-8), wherein M1Mass flow rate of fixed carbon in carbonaceous reducing agent, M2For SO in sulfur-containing flue gas2Mass flow rate of (d); preferably: the molar ratio S (0) of zero-valent sulfur to positive tetravalent sulfur in the process gas containing gaseous sulfur discharged from the carbonaceous reducing furnace is S (IV): 1.3-95: 1; further preferably: in the case of sulfur dusting, S (0): the ratio of S (IV) is not less than 1.05, and when sodium thiosulfate is generated, S (0): the ratio of S (IV) is controlled to be 1.05-1.08.
8. The method according to claim 5, wherein the temperature of the gaseous sulfur-containing process gas entering the high temperature dust collector in step ② is 380-650 ℃, and the temperature drop of the gas before and after entering the high temperature dust collector is not more than 30 ℃.
9. The method according to claim 5, wherein the condensation separator A in the step ③ uses process hot water at 103-108 ℃ or process gas at 70-105 ℃ as a cooling medium to cool the process gas containing the gaseous sulfur to 105-113 ℃, and the condensation separator B uses process water at 15-100 ℃ or process gas at less than 80 ℃ as a cooling medium to cool the process gas containing the gaseous sulfur to below 105 ℃.
10. The method according to claim 5, wherein the stirring is performed during the heating and curing process in step ⑤, the stirring speed is adjusted to 26-35 r/min, the reaction temperature is controlled to 100-105 ℃, and the reaction time is controlled to 30-45 min.
CN201911286382.8A 2019-12-13 2019-12-13 Sulfur dioxide recycling system and method Active CN111003692B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201911286382.8A CN111003692B (en) 2019-12-13 2019-12-13 Sulfur dioxide recycling system and method
US17/784,264 US11731874B2 (en) 2019-12-13 2020-05-10 System and method for resource recycling of sulfur dioxide
PCT/CN2020/089515 WO2021114561A1 (en) 2019-12-13 2020-05-10 System and method for resource recycling of sulfur dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911286382.8A CN111003692B (en) 2019-12-13 2019-12-13 Sulfur dioxide recycling system and method

Publications (2)

Publication Number Publication Date
CN111003692A true CN111003692A (en) 2020-04-14
CN111003692B CN111003692B (en) 2020-09-08

Family

ID=70115773

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911286382.8A Active CN111003692B (en) 2019-12-13 2019-12-13 Sulfur dioxide recycling system and method

Country Status (3)

Country Link
US (1) US11731874B2 (en)
CN (1) CN111003692B (en)
WO (1) WO2021114561A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489132A (en) * 2011-11-23 2012-06-13 武汉兴能环保技术有限公司 Novel dual-alkali desulfurization method for removal of sulfur dioxide from flue gas and generation of elemental sulfur as byproduct
CN104016382A (en) * 2014-06-27 2014-09-03 尚兰华 Method for producing sodium sulfite by desulfurizing flue gas by double-alkali process
WO2017004712A1 (en) * 2015-07-07 2017-01-12 Ionada Incorporated Improved membrane-based exhaust gas scrubbing method and system
CN106467293A (en) * 2016-09-19 2017-03-01 江苏德义通环保科技有限公司 A kind of method producing sulfur and the system and device producing sulfur
CN108557845A (en) * 2018-03-09 2018-09-21 杨奕颉 A kind of production method of sodium sulfite

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3667908A (en) * 1970-11-27 1972-06-06 Westvaco Corp Removal and recovery of sulfur oxides from gases
US4477426A (en) * 1983-04-29 1984-10-16 Foster Wheeler Energy Corporation Process for preparing a sulfur dioxide containing gas stream for reaction with coal
DE3407884A1 (en) * 1984-03-03 1985-09-05 Laboratorium für Adsorptionstechnik GmbH, 6000 Frankfurt METHOD FOR REMOVING SULFUR OXIDS FROM SMOKE GAS WITH REGENERABLE ACTIVE CARBON
CN104071759B (en) * 2014-06-13 2016-07-06 安徽佑骏商品混凝土有限公司 A kind of preparation method of sodium thiosulfate
CN105271132B (en) * 2015-09-29 2017-10-13 山东三维石化工程股份有限公司 The recovery technology of sulfur of SWSR 6 and device
US9988270B2 (en) * 2015-12-30 2018-06-05 Tessenderlo Kerley, Inc. Oxidation process for producing potassium thiosulfate
US10005667B2 (en) * 2015-12-30 2018-06-26 Tessenderlo Kerley, Inc. Sulfur dioxide scrubbing system and process for producing potassium products
CN106809807A (en) * 2016-11-30 2017-06-09 佛山市兴华源机械设备有限公司 A kind of preparation method of sodium thiosulfate
CN108939767B (en) * 2018-07-13 2021-04-20 中冶长天国际工程有限责任公司 Wet efficient purification method for flue gas containing elemental sulfur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102489132A (en) * 2011-11-23 2012-06-13 武汉兴能环保技术有限公司 Novel dual-alkali desulfurization method for removal of sulfur dioxide from flue gas and generation of elemental sulfur as byproduct
CN104016382A (en) * 2014-06-27 2014-09-03 尚兰华 Method for producing sodium sulfite by desulfurizing flue gas by double-alkali process
WO2017004712A1 (en) * 2015-07-07 2017-01-12 Ionada Incorporated Improved membrane-based exhaust gas scrubbing method and system
CN106467293A (en) * 2016-09-19 2017-03-01 江苏德义通环保科技有限公司 A kind of method producing sulfur and the system and device producing sulfur
CN108557845A (en) * 2018-03-09 2018-09-21 杨奕颉 A kind of production method of sodium sulfite

Also Published As

Publication number Publication date
WO2021114561A1 (en) 2021-06-17
US11731874B2 (en) 2023-08-22
CN111003692B (en) 2020-09-08
US20230046206A1 (en) 2023-02-16

Similar Documents

Publication Publication Date Title
CN102442650B (en) Method for producing sulfuric acid and co-producing calcium carbide by phosphogypsum
CN102367169B (en) Method for preparation of sulfuric acid and combined production of fine flour iron through calcination of coal-derived pyrite in presence of oxygen-rich air
CN102303883A (en) Method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurated gypsum
CN111498811B (en) Process and device for gypsum calcination and CO coupling carbon thermal reduction
CN109928415B (en) System and method for recovering calcium carbonate and sulfur by calcining gypsum
CN108178131B (en) SO in regenerated gas by active coke desulfurization2Fluidized bed device and method for recovering sulfur
CN109573955B (en) Device and process for preparing sulfur and recovering desulfurizer through sulfate carbon thermal reduction
CN1939840A (en) Tail gas treatment and reutilization for calcium carbide stove
CN107324288B (en) Comprehensive treatment and recycling process for acidic waste gypsum
CN108190843A (en) With SO in carbon-based material reduction and desulfurization resolution gas2The air flow bed and method of Recovered sulphur
CN101624197B (en) Technology for calcining and recycling magnesium desulfurizing byproduct containing magnesium sulfite
CN101979130B (en) Method for removing hydrogen sulfide from industrial gas in recycling way
CN109775666B (en) Device and method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction
CN103301744B (en) Desulfurization device and method for preparing sulfur particles by removing SO2 from flue gas
CN211169850U (en) Sulfur dioxide resource recycling system
CN109592647B (en) Process for preparing sulfur and recovering desulfurizing/nitre agent by sulfur/nitrate iron-carbon reduction
CN111003692B (en) Sulfur dioxide recycling system and method
CN108298507B (en) Method and device for treating sulfur-containing flue gas generated by calcining petroleum coke by using pyrite acid making device
CN115006982A (en) Method for desulfurizing and carbon-fixing coal-fired flue gas by using carbide slag slurry
CN108217606A (en) Utilize the cross-flow moving bed device of carbon-based material reduction and desulfurization resolution gas Recovered sulphur
CN109499344B (en) Calcium/magnesium-based wet desulphurization and calcium sulfite/magnesium sulfite resource utilization system and process
CN111097273B (en) Method and device for treating FCC (fluid catalytic cracking) regenerated flue gas
CN109529579B (en) Process device and process method for reaction desulfurization of hydrogen sulfide and sulfur dioxide
CN111573710A (en) System and method for removing hydrogen sulfide and co-producing calcium carbonate and sulfur from gypsum
CN206417874U (en) A kind of system and device that calcium oxide and sulphur are produced from gypsum

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant